Process for producing heavy hydrocarbon oils



Nov. 7, 1933. R. T. HASLAM PROCESS FOR PRODUCING HEAVY HYDROCARBON OILSFiled May 15, 1950 UNITED STATES PATENT OFFICE PROCESS FOR PRODUCINGHEAVY HYDROCARBON OILS Robert T. Haslam, Westfield, N. J., assignor toStandard-I. G. Company Application May 15, 1930. Serial No. 452,664

8 Claims. (01. 196-78) The present invention relates to a process formay or may not be operated depending upon improving hydrocarbon oils bytreatment with whether or not it is desired to operate tower 16 hydrogenunder elevated temperature and presunder a vacuum.

sure and applies specifically to an improved Oils of intermediatedensity and viscosity are process for the manufacture of high gradelubriwithdrawn from the tower in any suitable man- 60 eating oils fromreduced crude or suitable heavy ner, for example by pan and line 26 andare fractions. My invention will be fully understood forced by pump 27into heating coil 28. If from the following description and drawingdesired, oil from an external source may be which illustrates one formof apparatus suitable supplied to line 26 by line 29 and connection 13for carrying out my invention. 48. Hydrogen may be added to the oilentering 65 The drawing shows diagrammatically in seccoil 28 by line 30and/or by line 31. Heating tional elevation an apparatus constructed tocoil 28 is mounted in a suitable furnace setting carry out my inventionand indicates the flow of 32 and discharges through line 33 to reactionthe various materials in the process. drum 34 which is provided withinsulation 35 15 Referring to the drawing a hydrocarbon oil is anddesigned'to withstand temperatures of 750 fed from any convenient sourceby pump 1 into to 850 F. and pressures in excess of 200 atmosline 2where it joins a stream of gas rich in hypheres or more. The interior ofthe drum is drogen supplied by pipe 3. The mixture of oil filled with acatalytic material 36, which may and gas passes from line 2 to heatexchanger 4 or may not be of the same composition as catalyst 20 andthence-by line 5 to heating coil 6 mounted 11 in drum 9. Additionalhydrogen may be in a suitable furnace 7. The coil discharges added todrum 34 by means of line 37. The

through line 8 into reaction drum 9 which is prohydrogen and oil pass uptogether through vided with suitable insulation 10 and constructedcatalyst bed 36 and flow from the drum through to withstand temperaturesin the neighborhood line 38 and thence to heat exchanger 4 by means J of750 to 850 F. and pressures of 200 atmospheres of line 39. $0 or higher.The interior of the drum is filled It ill b understoodthat I may operatemy With a Cata yti at l 11 Which y be p c process using but one reactiondrum, whereby into th dru in a y ab manner, for eXamthe oils ofintermediate viscosity and density are p in Small lumps p trays-Additional recycled instead of. passing to a second drum.

30 hy r en as y be dd d to th dr y In this type of operation, the oilfrom pan 25 means of line 12. Th hydrogen and 011 Which would be passedthrough line 29 to pump 49 from is substant y all in the liquid p pass pwhich it would be recycled to coil 6 by means of simultaneously t r theCatalytic bed 11 lines 50 and 5. A portion of the stream in line wherethe oil is improved and a small percentage 29 would be drawn fi byconnectiqn 43 as fin.-

- of low boilin oils ar m d- These l w boiling ished light oil product.If it is desired to avoid oils, which consistof naphtha or kerosene andsending th hydrogen and apors from drum the like, pass out of the drumas a vapor through 9 through il 23 a d dr m 34, the valve 31a line 13 inmixtu e Wi t g sin line 31 may be closed and valve 40a in line Theliquid phase Oil is Withdrawn at the p 40 may be opened, whereby the gasand vapors of the drum by line 14 and conducted through f om drum 9 passthrough lines 13, 40, and 39 valv 15, wher h pressure is reduced, to flato heat exchanger 4. With valve 40a closed tower 16. Tower 16 m y bProvided With a and valve 3111 open materials in line 13 will at C011 17at the bottom and a cooling Coil pass to coil 28 and drum 34. Aftercooling in 18 at the top nd y Contain bubble p heat exchanger 4 the gasand oil pass to 45 other Suitab packing as needed- Heavy Oil separator41 where the gas is separated from the 1 product may be withdrawn fromthe bottom of oil, which oil may be withdrawn to storage the towerthrough line 19. A small amount of through line 42. Gas passes offthrough pipe light vapors and gas'dissolved in the oil with- 43 to asuitable purification system 44 for redrawn from the reactor pass fromthe tower by moving gaseous hydrocarbons and sulfur conmeans of line 20to cooler 21 where the vapors taining compounds, such as scrubbing withheavy are condensed. The condensate, which may conoils, soda ashsolution, and the like. The purisist of oils of a boiling range too lowfor lubrified gas flows to booster compressor 45 which cants, collectsin separator 22 from which it may discharges it into line 46. Fresh ormake-up be withdrawn. Separated gas is removed by line hydrogen issupplied to line 46 by compressor 23 which is provided with vacuum pump24 which 47. If desired gas passi from separator 22 y line 23 may beadded to the inlet supp y of compressor 47. The gas in line 46 passes'toline 3 for passage through the process as described.

In the operation of my improved process the feed stock consists of heavyhydrocarbon oils such as crudes or reduced crudes and may be stockscontaining but small amounts of asphaltic materials, for examplelubricating stocks.

It has been found that the lighter portions of the desired productobtained by the treatment of these feed stocks with hydrogen are notimproved to as great an extent as the heavier portionsu I thereforepropose to separate these lighter fractions of the desired product andsubject them to an additional stage of hydrogen treatment. The firsttreatment will be referred to as the primary stage, while that stage inwhich the lighter oils receive additional improvement will be known asthe secondary hydrogenation stage.

The feed is heated preferably with hydrogen, to a temperature notexceeding about 830 F. by rapid passage through a heated coil at a highrate sufiicient to prevent decomposition. The heated mixture then passesunder high pressure to thereaction drum of the primary stage. The drumis packed witha suitable catalyst which may comprise the oxides andsulfides of elements of the sixth group of the periodic table, theirmixtures with each other or with other compounds, such as zinc oxide,magnesia, lime or alumina, these being characterized by resistance tosulfur.

The primary reaction drum is preferably maintained at a temperature notin excess of 830 F. and ordinarily in the range between about I50 and810 F., the heat of coil 6 and the heat of the reaction being sufficientto maintain the temperature of the drum which is suitably insulated. Thepressure is held above about 20 atmospheres and preferably in excess ofabout 100 or 200 atmospheres, and may be as high as 1,000 atmospheres.An excess of hydrogen is used with the oil, preferably in the ratio ofabout 5,000 to 10,000 cubic feet of hydrogen per barrel of oil fed tothe process. The oil feed rate to the primary stage is expressed interms of the volume of the primary reaction drum and is preferably heldbetween 0.3 and 1.2 volumes of oil per volume of reaction drum per hour,the poorer qualities of feed oil requiring more time than higher gradeoils to produce equivalent products.

In their flow through the catalytic mass, reaction takes place betweenthe hydrogen and the oil, thereby yielding lubricating oils of highquality as regards flash, sulfur content, and color,

and which possess temperature-viscosity relationships tending towardthose of Pennsylvania petroleum as distinguished from oils of the Texascoastal class. A small amount of oil boiling below 400 F. is fonned inthe reactor as side reaction product, but does not ordinarily amount tomore than about 10 to 15 percent of the feed. The lubricating fractions,which comprise the major portion of the product,,usually containincreased amounts of light oils such as spindle oils, transformer oils,pale oils and the like, equivalent to about 5 to 50 percent of the feed.The amount of these light oils in the product is dependent on theseverity of the hydrogenation treatment and on the viscosity of thefeed, a light viscosity feed stock yielding a high percentage of theseoils while with more viscous charging stocks a smaller percentage isobtained. Similarly, a more intensive hydrogenation treatment produces alarger percentage of lower viscosity products, as will be understood.These low viscosity oils, as mentioned before, are not improved to theextent of the heavier fractions.

The product flowing from the primary reactor is therefore separated insuch a way that the lighter lubricating fractions may be sent to thesecondary hydrogenation stage. This separation may be carried out by anysuitable means, for example by passing the product to a flash tower at areduced pressure, from which several streams may be withdrawn. Ifdesired this separation may take place in the presence of the hydrogengas which passes through the primary reactor with the feed, or the gastogether with a small amoun'; of vapor formed in the process may bedrawn off the reactor separately from the liquid oil as shown indrawing. The heavier fractions of the product are withdrawn from-theprocess at this point while the lighter fractions, consisting of spindleoils, transformer oils, and the like are transferred to the secondaryhydrogenation stage where they are subjected to treatment in apparatussimilar to that in the primary stage.

The hydrogen used in the secondary stage may consist of that used in theprimary stage, or fresh hydrogen, or both, may be employed. As in theprimary stage, the hydrogen is used in excess, in an amount equivalentto about 5,000 to 10,000 cubic feet per barrel of oil. The oil ispreheated, preferably in admixture with the hydrogen, and passed intothe secondary reaction drum. This drum is packed with a suitablecatalyst which may or may not be of the same composition as that in theprimary reactor, but which preferably consists of the oxides or sulfidesof the elements of the sixth group, their mixtures with each other, orwith other compounds such as zinc .oxide, lime, magnesia or alumina. Thereactor is maintained at a temperature preferably between 750 and 810 F.

The pressure employed may be the same as that used in the primaryreactor and is ordinarily in" excess of 100, 200 or even 1,000atmospheres. If a highly hydrogenating action is desired in thesecondary reactor a pressure in excess of that in the primary stage maybe used. The feed rate to the secondary reactor is dependent on thedegree of improvement desired in the product and is lower for greaterimprovement, as will be understood. In general, the feed rate may betaken between 0.3 and 1.2 volumes of oil per volume of reactor per hour.

By utilization of this additiona :tage of treatment for the lighteroils, it is possible to improve them as regards flash,temperature-viscosity relationships, etc. in proportion with thatobfainecl in the heavier oils, and if desired they may be improved to agreater extent. It will be understood that I may' also substantiallysecure the same result by employing only one reaction stage in whichcase the light oils are re-passed one or more times through the reactorand the heavier oils are withdrawn after one passage. The method ofcarrying out this type of operation with the apparatus shown inthedrawing has been lowing claims in which it is wished to claim allnovelty inherent in this invention.

I claim.

1. In a process for preparing lubricating oils of high quality bysubjecting heavy hydrocarbon oils to the action of a gas rich in freehydrogen at temperatures between 750 and 810 F. and under pressure inexcess of 50 atmospheres for a limited time whereby an appreciablebutrestricted quantity of low boiling hydrocarbons is formed, theimprovement which comprises conducting the treatment with hydrogen intwo separate zones, removing the heavier lubricating fractions from theproducts of the first zone and forwarding only the lighter lubricatingfra tions to the second zone.

2. In a process for preparing lubricating oils of high quality fromheavy hydrocarbon oils by subjecting such heavy hydrocarbon oils to theaction of a gas rich in free hydrogen in a reaction zone maintained attemperatures between 750 and 810 F. and under pressure in excess of 50atmospheres for a limited time whereby an appreciable but restrictedquantity of low boiling hydrocarbons is formed, the improvement whichcomprises separating the lighter lubricating fractions from the productsof the treatment and returning these lighter fractions to the reactionzone for further treatment.

3. Process according to claim 1 in which the lighter lubricatingfractions are separated from the heavier lubricating fractions byreducing pressure on the liquid product withdrawn from the first zonewhereby the lighter lubricating fractions are caused to vaporize.

4. Process according to claim 2 in whichthe lighter lubricatingfractions are separated from the heavier lubricating fractions byreduction of pressure on the liquid products withdrawn from the reactionzone whereby the lighter lubricating fractions are caused to vaporize.

5. An improved process for preparing lubricating oils of high qualityfrom heavy hydrocarbon oils which comprises subjecting such heavy oilsto the action of a gas rich in free hydrogen in a reaction zonemaintained at a temperature between 750 and 810 F. and under a pressurein excess of 50 atmospheres for a limited time whereby an appreciablebut restricted quantity of low boiling hydrocarbons is formed,continuously removing vapors therefrom, separately withdrawing liquidproducts from the reaction zone, separating the lighter lubricatingfractions therefrom and subjecting these lighter fractions to furthertreatment with hydrogen under substantially the same conditions.

6. Process according to claim 5 in which the liquid product withdrawnfrom the reaction zone is introduced into a rectification zonemaintained under a substantially lower pressure than the reaction zonewherein the lighter lubricating fractions are separated from thehyrocarbons boiling in the motor fuel range and the high boiling heavylubricating fractions.

7. Process according to claim 5 in which the treatment with hydrogen'is' carried out in the presence of a catalytic material which promotesthe hydrogenation.

8. Process according to claim 5 in which the reaction zone is maintainedunder pressure in excess of 100 atmospheres.

ROBERT T. HASLAM.

